US9688864B2 - Pumpable shelf-stable suspension of fibers in an organic phase - Google Patents

Pumpable shelf-stable suspension of fibers in an organic phase Download PDF

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US9688864B2
US9688864B2 US14/902,255 US201414902255A US9688864B2 US 9688864 B2 US9688864 B2 US 9688864B2 US 201414902255 A US201414902255 A US 201414902255A US 9688864 B2 US9688864 B2 US 9688864B2
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pumpable
shelf
stable suspension
fibers
suspension according
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Bernhard FEICHTENSCHLAGER
Radoslaw Kierat
Christian Buchner
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/027—Dispersing agents
    • B01F17/0042—
    • B01F17/005—
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/10—Homopolymers or copolymers of propene
    • C09D123/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/16—Amines or polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/018—Additives for biodegradable polymeric composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds

Definitions

  • the present invention relates to a pumpable shelf-stable suspension of fibers in an organic phase and also to a method of using a disubstituted urea to suspend fibers in an organic phase.
  • the problem addressed by the present invention was that of substantially resolving the aforementioned issues.
  • the problem was more particularly that of providing a fiber preparation which is readily handleable, ideally conveyable mechanically and does not throw a sediment even in the course of prolonged storage.
  • the problem addressed was more particularly that of providing the pumpable shelf-stable suspension of the present invention.
  • disubstituted ureas are able to stabilize a multiplicity of fibers permanently and in the form of a pumpable suspension.
  • the present invention accordingly provides in a first aspect a pumpable shelf-stable suspension of fibers in an organic phase, comprising 1.0-60 wt % of fibers, and 0.01-10 wt % of a disubstituted urea (the organic phase comprises the remainder).
  • the suspension can additionally comprise further ingredients, in which case all percentages have to sum to 100 wt %, as will be appreciated.
  • the suspension of the present invention comprises 10-60 wt %, especially 25-50 wt % of fibers.
  • suspension of the present invention comprises 0.05-10 wt %, especially 0.1-5 wt % of the disubstituted urea.
  • an “organic phase” is generally any liquid organic compound that is not miscible with water. Not miscible with water is to be understood in this context as meaning that two phases form in the organic compound/water system. More particularly, said organic compound shall have a solubility in water at 20° C. of less than 10 wt %, preferably less than 2 wt % and especially less than 1 wt %.
  • Organic phase is preferably to be understood as meaning, by contrast, a mineral oil, crude oil, paraffin oil, benzine, petroleum, naphthenic oil, aromatic oil, an aliphatic or aromatic hydrocarbon such as, for example, benzene, toluene and xylene, a fatty oil (triglyceride), a fatty acid ester such as, for example, biodiesel, a silicone oil, but also customary plasticizers such as, for example, various phthalate esters and hydrogenated phthalate esters.
  • the “organic phase” can further also be a reactive component for polymer formation, for example an acrylate or an isocyanate. Mixtures of two or more of these compounds can also be used, however. Aliphatic and aromatic hydrocarbons are very particularly preferred.
  • Fibers are flexible structures which are thin compared with their length in that they have a length/diameter ratio of preferably not less than 10:1 and more preferably of not less than 100:1.
  • Fibers suitable for the purposes of the present invention can consist of a multiplicity of different materials, for example of polyolefins comprising polyethylene and polypropylene; polyvinyl alcohol; polyacrylonitrile; polyesters comprising polyglycol adipate, polyethylene terephthalate, polylactic acid (PLA); polyamides comprising polycaprolactam, nylon 66, nylon 6T; inorganic materials comprising glass, carbon, basalt and metals; or renewable materials comprising cellulose and lignin; and mixtures thereof.
  • the fibers conveniently have diameters of 2 ⁇ m to 2 mm, preferably 10 ⁇ m to 100 ⁇ m, and lengths of conveniently 0.1 mm to 25 cm, preferably of 1 mm to 10 cm, subject to the proviso of an aspect ratio (length/diameter ratio) of not less than 10, preferably not less than 100.
  • Particularly preferred chopped fibers are not more than 2.5 cm in length.
  • the “disubstituted urea” is obtainable from a monoisocyanate or polyisocyanate and an organic amine.
  • the monoisocyanate conforms to the formula R 1 —NCO, where R 1 is preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, 2-ethyl-n-hexyl, n-lauryl, cyclohexyl, phenyl and benzyl.
  • the polyisocyanate is preferably an aliphatic isocyanate, an aromatic isocyanate or a combined aliphatic-aromatic isocyanate having an NCO functionality (number of NCO groups in the molecule) from 2 to 5, preferably from 2 to 3.
  • Suitable polyisocyanates comprise tetramethylene 1,4-diisocyanate, 2-methyl-pentamethylene 1,5-diisocyanate, hexamethylene 1,6-diisocyanate (HDI), 2,2,4- and 2,4,4-trimethylhexamethylene 1,6-diisocyanate (TMDI), dodecamethylene 1,12-diisocyanate, lysine diisocyanate, lysine ester diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate—IPDI), 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), 2,2′-, 2,4′- and 4,4′-dicyclohexylmethane diisocyanate (H 12 MDI), cyclohexane 1,3-diisocyanate and cyclohexane 1,
  • the polyisocyanates of the present invention shall also comprise dimers (uretdiones) and trimers (isocyanurates).
  • the “organic amine” is preferably an unsubstituted unbranched, branched or cyclic, saturated or olefinically mono- or polyunsaturated primary amine, preferably a primary aliphatic amine and especially a fatty amine.
  • the present invention has been found to work particularly well with C 6-22 alkylamines, especially oleylamine and this especially in combination with MDI.
  • the disubstituted urea obtainable by reacting the isocyanate with the organic amine is either prepared directly in the organic phase or prepared in a solvent and obtained as redissolvable powder by drying.
  • the present invention further provides the method of using said disubstituted urea to suspend fibers in said organic phase.
  • oleylamine 100 g were dissolved in 300 g of toluene. Under vigorous agitation, 46.77 g of MDI (Lupranat® MI from BASF SE—isomer mixture) were dissolved in 300 g of toluene in another vessel and gradually (the temperature rises) added to the oleylamine solution. Agitation was continued for a further 30 min before the solvent was evaporated to obtain the product as a whitish waxy powder.
  • MDI Liquiranat® MI from BASF SE—isomer mixture
  • a suspension was prepared from 50 ml of paraffin oil (C 11-25 fraction), 3.0 g of product from Example 1 and 40 g of polylactic acid fibers (about 6 mm in length, ⁇ 20 ⁇ m in thickness) and stored in a screw lid jar for 3 hours or 1 week. There was no observable sedimentation of fibers. Suspension pumpability was tested using a pressure-driven cartridge press. Using a pumping pressure of 1 bar, a hole diameter of 20 mm and a cartridge diameter of 4.6 cm, an 80.1 g quantity of the suspension could be pumped within 3 seconds (26.7 g/s). No observable separation occurred during pumping.
  • Example 3 was repeated with different fibers, solvents and dispersants. The results are shown in table 1 (storage tests) and table 2 (pumping tests). Hand pumping was used in contrast to Example 3. It is apparent that only the disubstituted ureas of the present invention solve the problem defined at the beginning, and that oleylamine combined with MDI works best.
  • Lutensol ® GD 70 BASF SE-alkylpolyglucoside surfactant
  • Triton ® H 66 Dow Chemicals-anionic phosphate polyether surfactant
  • Sovermol ® 920 BASF SE-branched polyether polyol Disperbyk ® 180: dispersing additive for organic systems, from Byk BYK ® W 980: dispersing additive for organic resins, from Byk Desmodur ® N 3600: Bayer AG, HDI trimer

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paper (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A pumpable shelf-stable suspension of fibers in an organic phase comprising 1.0-60 wt % of fibers and 0.01-10 wt % of a disubstituted urea is proposed as well as a method using the disubstituted urea to suspend fibers in an organic phase.

Description

This application is a §371 of International Application No. PCT/EP2014/061971 filed Jun. 10, 2014, and claims priority from European Patent Application No. 13178707.9 filed Jul. 31, 2013.
The present invention relates to a pumpable shelf-stable suspension of fibers in an organic phase and also to a method of using a disubstituted urea to suspend fibers in an organic phase.
The production of fiber-containing coatings, floorcoverings, tires, artificial leathers and the like generally requires the metered addition of fibers. Handling these fibers is often difficult. Especially when fibers are to be added to oily, hydrophobic liquids, unwelcome issues can arise because of insufficient suspendability on the part of the fibers, possibly also due to electrostatic effects, due to clumping of the fibers (known as “birdnesting”), etc. It is also the case that these kinds of fibers, in particular chopped fibers, are often difficult to convey. Batchwise addition, possibly by hand, to organic formulations in particular, by contrast, is associated with increased labor requirements and hence increased costs.
The problem addressed by the present invention was that of substantially resolving the aforementioned issues. The problem was more particularly that of providing a fiber preparation which is readily handleable, ideally conveyable mechanically and does not throw a sediment even in the course of prolonged storage. The problem addressed was more particularly that of providing the pumpable shelf-stable suspension of the present invention.
The problem is solved by the features of the independent claims. The dependent claims relate to preferred embodiments of the present invention.
It was found that, surprisingly, disubstituted ureas are able to stabilize a multiplicity of fibers permanently and in the form of a pumpable suspension.
The present invention accordingly provides in a first aspect a pumpable shelf-stable suspension of fibers in an organic phase, comprising 1.0-60 wt % of fibers, and 0.01-10 wt % of a disubstituted urea (the organic phase comprises the remainder). The suspension can additionally comprise further ingredients, in which case all percentages have to sum to 100 wt %, as will be appreciated.
Preferably, the suspension of the present invention comprises 10-60 wt %, especially 25-50 wt % of fibers.
It is further preferable for the suspension of the present invention to comprise 0.05-10 wt %, especially 0.1-5 wt % of the disubstituted urea.
For the purposes of the present invention, an “organic phase” is generally any liquid organic compound that is not miscible with water. Not miscible with water is to be understood in this context as meaning that two phases form in the organic compound/water system. More particularly, said organic compound shall have a solubility in water at 20° C. of less than 10 wt %, preferably less than 2 wt % and especially less than 1 wt %.
“Organic phase” is preferably to be understood as meaning, by contrast, a mineral oil, crude oil, paraffin oil, benzine, petroleum, naphthenic oil, aromatic oil, an aliphatic or aromatic hydrocarbon such as, for example, benzene, toluene and xylene, a fatty oil (triglyceride), a fatty acid ester such as, for example, biodiesel, a silicone oil, but also customary plasticizers such as, for example, various phthalate esters and hydrogenated phthalate esters. The “organic phase” can further also be a reactive component for polymer formation, for example an acrylate or an isocyanate. Mixtures of two or more of these compounds can also be used, however. Aliphatic and aromatic hydrocarbons are very particularly preferred.
“Fibers” are flexible structures which are thin compared with their length in that they have a length/diameter ratio of preferably not less than 10:1 and more preferably of not less than 100:1. Fibers suitable for the purposes of the present invention can consist of a multiplicity of different materials, for example of polyolefins comprising polyethylene and polypropylene; polyvinyl alcohol; polyacrylonitrile; polyesters comprising polyglycol adipate, polyethylene terephthalate, polylactic acid (PLA); polyamides comprising polycaprolactam, nylon 66, nylon 6T; inorganic materials comprising glass, carbon, basalt and metals; or renewable materials comprising cellulose and lignin; and mixtures thereof.
The fibers conveniently have diameters of 2 μm to 2 mm, preferably 10 μm to 100 μm, and lengths of conveniently 0.1 mm to 25 cm, preferably of 1 mm to 10 cm, subject to the proviso of an aspect ratio (length/diameter ratio) of not less than 10, preferably not less than 100. Particularly preferred chopped fibers are not more than 2.5 cm in length.
The “disubstituted urea” is obtainable from a monoisocyanate or polyisocyanate and an organic amine. The monoisocyanate conforms to the formula R1—NCO, where R1 is preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, 2-ethyl-n-hexyl, n-lauryl, cyclohexyl, phenyl and benzyl. The polyisocyanate is preferably an aliphatic isocyanate, an aromatic isocyanate or a combined aliphatic-aromatic isocyanate having an NCO functionality (number of NCO groups in the molecule) from 2 to 5, preferably from 2 to 3. Suitable polyisocyanates comprise tetramethylene 1,4-diisocyanate, 2-methyl-pentamethylene 1,5-diisocyanate, hexamethylene 1,6-diisocyanate (HDI), 2,2,4- and 2,4,4-trimethylhexamethylene 1,6-diisocyanate (TMDI), dodecamethylene 1,12-diisocyanate, lysine diisocyanate, lysine ester diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate—IPDI), 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), 2,2′-, 2,4′- and 4,4′-dicyclohexylmethane diisocyanate (H12MDI), cyclohexane 1,3-diisocyanate and cyclohexane 1,4-diisocyanate (CHDI), 1,3- and 1,4-bis(isocyanatomethyl)-cyclohexane, 4,4′-diisocyanatodicyclohexyl-2,2-propane, m- and p-phenylene diisocyanate, 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl (TOBI), 2,4- and 2,6-tolylene diisocyanate (TDI), 2,2′-, 2,4′- and 4,4′-diphenylmethane diisocyanate (MDI), naphthalene 1,2-diisocyanate and naphthalene 1,5-diisocyanate (NDI), m- and p-xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), and also any desired mixtures thereof. For the purposes of the present invention, the polyisocyanates of the present invention shall also comprise dimers (uretdiones) and trimers (isocyanurates). The HDI trimer is particularly important here. Oligomers shall further also be comprehended, an example being “polymeric MDI” where n=1 to 8:
Figure US09688864-20170627-C00001
The “organic amine” is preferably an unsubstituted unbranched, branched or cyclic, saturated or olefinically mono- or polyunsaturated primary amine, preferably a primary aliphatic amine and especially a fatty amine.
The present invention has been found to work particularly well with C6-22alkylamines, especially oleylamine and this especially in combination with MDI.
The disubstituted urea obtainable by reacting the isocyanate with the organic amine is either prepared directly in the organic phase or prepared in a solvent and obtained as redissolvable powder by drying.
The present invention further provides the method of using said disubstituted urea to suspend fibers in said organic phase.
The examples which follow illustrate the invention.
EXAMPLES Example 1: Reaction of Oleylamine with MDI
100 g of oleylamine were dissolved in 300 g of toluene. Under vigorous agitation, 46.77 g of MDI (Lupranat® MI from BASF SE—isomer mixture) were dissolved in 300 g of toluene in another vessel and gradually (the temperature rises) added to the oleylamine solution. Agitation was continued for a further 30 min before the solvent was evaporated to obtain the product as a whitish waxy powder.
Example 2: Reaction of Oleylamine with MDI
34.07 g of oleylamine were mixed with 600 g of paraffin oil (C11-25 fraction) under vigorous agitation. Under vigorous agitation, 15.93 g (Lupranat® MI from BASF SE—isomer mixture) were dissolved in 300 g of toluene in another vessel and gradually added to the oleylamine solution (slight rise in temperature). Agitation was continued for a further 30 min to obtain the product as a colorless, slightly opaque, viscous, thixotropic but nonetheless pressure-pumpable solution.
Example 3: Properties of Fiber Suspension According to the Present Invention
A suspension was prepared from 50 ml of paraffin oil (C11-25 fraction), 3.0 g of product from Example 1 and 40 g of polylactic acid fibers (about 6 mm in length, <20 μm in thickness) and stored in a screw lid jar for 3 hours or 1 week. There was no observable sedimentation of fibers. Suspension pumpability was tested using a pressure-driven cartridge press. Using a pumping pressure of 1 bar, a hole diameter of 20 mm and a cartridge diameter of 4.6 cm, an 80.1 g quantity of the suspension could be pumped within 3 seconds (26.7 g/s). No observable separation occurred during pumping.
Example 4: Various Test Series
Example 3 was repeated with different fibers, solvents and dispersants. The results are shown in table 1 (storage tests) and table 2 (pumping tests). Hand pumping was used in contrast to Example 3. It is apparent that only the disubstituted ureas of the present invention solve the problem defined at the beginning, and that oleylamine combined with MDI works best.
TABLE 1
Amount
Test Amount of of Fiber Fiber Stab. Stab. Stab.
No. Dispersant dispersant Solvent solvent type quantity 1 h 24 h 14 d Comments
1 none paraffin oil  50 ml PLA, PP 10 g no no no unbrushable, separates
2 none aromatics  50 ml PLA, PP 10 g no no no unbrushable, separates
3 Lutensol ® GD 70 1 g aromatics 100 ml PLA, PP  3 g no no no unbrushable, separates
4 Triton ® CG 110 1 g aromatics 100 ml PLA, PP  3 g no no no unbrushable, separates
5 Triton ® H 66 1 g aromatics 100 ml PLA, PP  3 g no no no unbrushable, separates
6 sodium dodecylsulfate 1 g aromatics 100 ml PLA, PP  3 g no no no unbrushable, separates
7 Sovermol ® 1111 1 g aromatics 100 ml PLA, PP  3 g no no no unbrushable, separates
8 Sovermol ® 920 1 g aromatics 100 ml PLA, PP  3 g no no no unbrushable, separates
9 methyl laurate 1 g aromatics 100 ml PLA, PP  3 g no no no unbrushable, separates
10 butyl acetate 1 g aromatics 100 ml PLA, PP  3 g no no no unbrushable, separates
11 BYK ® 306 1 g aromatics 100 ml PLA, PP  3 g no no no unbrushable, separates
12 Disperbyk ® 180 1 g aromatics 100 ml PLA, PP  3 g no no no unbrushable, separates
13 BYK ® W 980 1 g aromatics 100 ml PLA, PP  3 g no no no unbrushable, separates
14 DBE-IB 1 g aromatics 100 ml PLA, PP  3 g no no no unbrushable, separates
15 castor oil 1 g aromatics 100 ml PLA, PP  3 g no no no unbrushable, separates
16 oleylamine-Lupranat ® MI 1 g aromatics 100 ml PLA  3 g yes yes yes thickening effect, brushable
17 oleylamine-Lupranat ® MI 1 g aromatics 100 ml PLA 20 g yes yes yes thickening effect, brushable
18 oleylamine-Lupranat ® MI 2 g aromatics 100 ml PLA 10 g yes yes yes thickening effect, brushable
19 oleylamine-Lupranat ® MI 2 g aromatics 100 ml PLA 30 g yes yes yes thickening effect, brushable
20 oleylamine-Lupranat ® MI 4 g aromatics 100 ml PLA  3 g yes yes yes thickening effect, brushable
21 oleylamine-Lupranat ® MI 4 g aromatics 100 ml PLA 10 g yes yes yes thickening effect, brushable
22 oleylamine-Lupranat ® MI 1 g paraffin oil  50 ml PLA 20 g yes yes yes thickening effect, brushable
23 oleylamine-Lupranat ® MI 1 g paraffin oil  50 ml PLA 30 g yes yes yes thickening effect, brushable
24 oleylamine-Lupranat ® MI 2 g paraffin oil  50 ml PLA 20 g yes yes yes thickening effect, brushable
25 oleylamine-Lupranat ® MI 2 g paraffin oil  50 ml PLA 30 g yes yes yes thickening effect, brushable
26 oleylamine-Lupranat ® MI 3 g paraffin oil  50 ml PLA 40 g yes yes yes thickening effect, brushable
27 oleylamine-Lupranat ® MI 2 g paraffin oil  50 ml PP 10 g yes yes yes thickening effect, brushable
28 oleylamine-Lupranat ® MI 2 g paraffin oil  50 ml PVA 10 g yes yes yes thickening effect, brushable
29 oleylamine-Lupranat ® MI 2 g paraffin oil  50 ml cellulose 10 g yes yes yes thickening effect, brushable
30 octadecylamine-Lupranat ® MI 5 g paraffin oil  50 ml PLA, PP 20 g yes yes yes minimal sedimentation
31 ethylhexylamine-Lupranat ® MI 5 g paraffin oil  50 ml PLA, PP 20 g yes yes yes minimal sedimentation
32 oleylamine-Desmodur ® N3600 3 g paraffin oil  50 ml PLA, PP 10 g yes no no stable for some hours
33 tallowamine-Lupranat ® MI 3 g paraffin oil  50 ml PLA, PP 10 g yes yes yes moderately thickening effect
Legend
paraffin oil: C11-25 fraction
PLA: polylactic acid fibers, about 6 mm in length, <20 μm in thickness
PLA, PP: the two fiber types were tested separately
cellulose: cellulose fibers, approximately identical dimensions
Triton ® CG 110: Dow Chemicals ® alkylpolyglucoside surfactant
Sovermol ® 1111: BASF SE-branched polyether polyol
BYK ® 306: silicone surfactant from Byk
DBE-IB: high-boiling oxygenated solvent-containing diisobutyl adipate, glutarate
and succinate mixture from Invista
Lupranat ® MI: BASF SE-MDI isomer mixture
tallowamine: aminated animal tallow (fatty amine)
aromatics: mixture of C9 aromatics
PP: polypropylene fibers, approximately identical dimensions
PVA: polyvinyl alcohol fibers, approximately ca. identical dimensions
Lutensol ® GD 70: BASF SE-alkylpolyglucoside surfactant
Triton ® H 66: Dow Chemicals-anionic phosphate polyether surfactant
Sovermol ® 920: BASF SE-branched polyether polyol
Disperbyk ® 180: dispersing additive for organic systems, from Byk
BYK ® W 980: dispersing additive for organic resins, from Byk
Desmodur ® N 3600: Bayer AG, HDI trimer
TABLE 2
Amount Pumped
Test Amount of of Fiber quantity Pumping Ejection
No. Dispersant dispersant Solvent solvent Fiber type quantity [%] time hole Comments
1 oleylamine-Lupranat ® MI 2 g aromatics 100 ml  PLA 30 g 70% 10 s Ø 1 cm hole clogs up
2 oleylamine-Lupranat ® MI 4 g aromatics 100 ml  PLA 10 g 70% 10 s Ø 1 cm ejection almost
complete before
clogging
3 oleylamine-Lupranat ® MI 1 g paraffin oil 50 ml PLA 10 g 96% 10 s Ø 2 cm works very well,
homogeneous extrudate
4 oleylamine-Lupranat ® MI 1 g paraffin oil 50 ml PLA 20 g 96% 10 s Ø 2 cm works very well,
homogeneous extrudate
5 oleylamine-Lupranat ® MI 2 g paraffin oil 50 ml PLA 20 g 96% 10 s Ø 2 cm works very well,
homogeneous extrudate
6 oleylamine-Lupranat ® MI 2 g paraffin oil 50 ml PLA 25 g 96% 10 s Ø 2 cm works very well,
homogeneous extrudate
7 oleylamine-Lupranat ® MI 1 g paraffin oil 50 ml PLA 30 g 96% 10 s Ø 2 cm works poorly, clogs up,
too little dispersant
8 oleylamine-Lupranat ® MI 2 g paraffin oil 50 ml PP 10 g 96% 10 s Ø 2 cm works very well,
homogeneous extrudate
9 oleylamine-Lupranat ® MI 2 g paraffin oil 50 ml PVA 10 g 96% 10 s Ø 2 cm works very well,
homogeneous extrudate
10 oleylamine-Lupranat ® MI 2 g paraffin oil 50 ml cellulose 10 g 96% 10 s Ø 2 cm works very well,
homogeneous extrudate
11 oleylamine-Lupranat ® MI 2 g paraffin oil 50 ml PLA 30 g 96% 10 s Ø 2 cm works very well,
homogeneous extrudate
12 oleylamine-Lupranat ® MI 3 g paraffin oil 50 ml PLA 40 g 96% 10 s Ø 2 cm works very well,
homogeneous extrudate
13 oleylamine-Lupranat ® MI 2.5 g   paraffin oil 50 ml PLA 50 g 90% 10 s Ø 2 cm still works fairly well,
homogeneous extrudate
Legend as for Table 1

Claims (15)

What is claimed is:
1. A pumpable shelf-stable suspension of fibers in an organic phase, comprising:
1.0-60 wt % of fibers; and
0.01-10 wt % of a disubstituted urea.
2. The pumpable shelf-stable suspension according to claim 1, wherein the fibers are present in an amount of from 10-60 wt %.
3. The pumpable shelf-stable suspension according to claim 1, wherein the fibers are present in an amount of from 25-50 wt %.
4. The pumpable shelf-stable suspension according to claim 1, wherein the disubstituted urea is present in an amount of from 0.05-10 wt %.
5. The pumpable shelf-stable suspension according to claim 1, wherein the disubstituted urea is present in an amount of from 0.1-5 wt %.
6. The pumpable shelf-stable suspension according to claim 1, wherein the organic phase comprises at least one member selected from the group consisting of mineral oil, crude oil, paraffin oil, benzene, petroleum, a naphthenic oil, an aromatic oil, an aliphatic hydrocarbon, an aromatic hydrocarbon, a fatty oil, a fatty acid ester, a silicone oil and a phthalate ester.
7. The pumpable shelf-stable suspension according to claim 1, wherein the fibers comprise a material selected from the group consisting of a polyolefin, a polyester, a polyvinyl alcohol, a polyacetonitrile, a polyamide, polyethylene terephthalate, a polylactic acid, nylon 66 and nylon 6T.
8. The pumpable shelf-stable suspension according to claim 1, wherein the fibers comprise at least one material selected from the group consisting of polyethylene, polypropylene, polyglycol adipate and polycaprolactam.
9. The pumpable shelf-stable suspension according to claim 1, wherein the fibers comprise an inorganic material.
10. The pumpable shelf-stable suspension according to claim 9, wherein the inorganic material comprises at least one member selected from the group consisting of glass, carbon, basalt and a metal.
11. The pumpable shelf-stable suspension according to claim 1, wherein the fibers comprise a member selected from the group consisting of a renewable material, wherein said renewable material comprises a member selected from the group consisting of cellulose and lignin.
12. The pumpable shelf-stable suspension according to claim 1, wherein the fibers have a diameter of from 2 μm to 2 mm subject to the proviso of an aspect ratio of not less than 10.
13. The pumpable shelf-stable suspension according to claim 1, wherein the disubstituted urea is obtained from a monoisocyanate or polyisocyanate and a fatty amine.
14. The pumpable shelf-stable suspension according to claim 1, wherein the disubstituted urea is obtained from oleylamine and diphenylmethane diisocyanate (MDI).
15. A method of preparing the pumpable shelf-stable suspension according to claim 1 comprising adding to a mixture of the fibers in the organic phase the disubstituted urea.
US14/902,255 2013-07-31 2014-06-10 Pumpable shelf-stable suspension of fibers in an organic phase Expired - Fee Related US9688864B2 (en)

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PCT/EP2014/061971 WO2015014520A1 (en) 2013-07-31 2014-06-10 Pumpable suspension of fibres in an organic phase, said suspension having a long shelf-life

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